EVALUATING THE EFFECTIVENESS OF CONSERVATION WATER-PRICING PROGRAMS: REPLY

Resource /Energy Economics and Policy,

EVALUATING THE EFFECTIVENESS OF CONSERVATION WATER-PRICING PROGRAMS

Charging farmers increasing block prices for irrigation deliveries is advocated as a means of encouraging agricultural water conservation in the West. We formulated a model of a hypothetical irrigated river basin to investigate the hyrdro-economic circumstances in which such pricing leads to water conservation. Our results indicate that increasing delivery prices may encourage irrigators to make adjustments with countervailing impacts on consumptive water use and conservation. Whether these countervailing impacts combine to conserve water or increase its consumptive use must be resolved empirically. An alternative resolution of this ambiguity is to assess water prices in terms of consumptive use.Resource /Energy Economics and Policy,

Heterobimetallic ruthenium–zinc complexes with bulky N-heterocyclic carbenes: syntheses, structures and reactivity

The ruthenium–zinc heterobimetallic complexes, [Ru(IPr)2(CO)ZnMe][BArF4] (7), [Ru(IBiox6)2(CO)(THF) ZnMe][BArF4] (12) and [Ru(IMes)’(PPh3)(CO)ZnMe] (15), have been prepared by reaction of ZnMe2 with the ruthenium N-heterocyclic carbene complexes [Ru(IPr)2(CO)H][BArF4] (1), [Ru(IBiox6)2(CO)(THF)H][BArF4] (11) and [Ru(IMes)(PPh3)(CO)HCl] respectively. 7 shows clean reactivity towards H2, yielding [Ru(IPr)2(CO) (¿2-H2)(H)2ZnMe][BArF4] (8), which undergoes loss of the coordinated dihydrogen ligand upon application of vacuum to form [Ru(IPr)2(CO)(H)2ZnMe][BArF4] (9). In contrast, addition of H2 to 12 gave only a mixture of products. The tetramethyl IBiox complex [Ru(IBioxMe4)2(CO)(THF)H][BArF4] (14) failed to give any isol- able Ru–Zn containing species upon reaction with ZnMe2. The cyclometallated NHC complex [Ru(IMes)’ (PPh3)(CO)ZnMe] (15) added H2 across the Ru–Zn bond both in solution and in the solid-state to afford [Ru(IMes)’(PPh3)(CO)(H)2ZnMe] (17), with retention of the cyclometallati

N-Heterocyclic Carbene Non-Innocence in the Catalytic Hydrophosphination of Alkynes

Studies on alkyne hydrophosphination employing nickel-NHC catalysts (NHC=N-heterocyclic carbene) revealed that the free N-alkyl substituted NHCs themselves were catalytically active. DFT calculations showed the mechanism involves the NHC acting as a Brønsted base to form an imidazolium phosphide species which then undergoes rate-limiting nucleophilic attack at the terminal alkyne carbon. This mechanism explains the preference seen experimentally for reactions with aryl substituted phosphines and alkynes, while the rearrangements of the alkenyl anion formed upon P−C bond formation account for the observation of both Z- and E-regioisomers of the products.</p

N-Heterocyclic Carbene Non-Innocence in the Catalytic Hydrophosphination of Alkynes

Studies on alkyne hydrophosphination employing nickel-NHC catalysts (NHC=N-heterocyclic carbene) revealed that the free N-alkyl substituted NHCs themselves were catalytically active. DFT calculations showed the mechanism involves the NHC acting as a Bronsted base to form an imidazolium phosphide species which then undergoes rate-limiting nucleophilic attack at the terminal alkyne carbon. This mechanism explains the preference seen experimentally for reactions with aryl substituted phosphines and alkynes, while the rearrangements of the alkenyl anion formed upon P-C bond formation account for the observation of both Z- and E-regioisomers of the products

Stoichiometric and catalytic C-F bond activation by the<i> trans</i>-dihydride complex [Ru(IEt₂Me₂)₂(PPh₃)₂H₂] (IEt₂Me₂ = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)

The room temperature reaction of C6F6 or C6F5H with [Ru(IEt2Me2)2(PPh3)2H2] (1; IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene) generated a mixture of the trans-hydride fluoride complex [Ru(IEt2Me2)2(PPh3)2HF] (2) and the bis-carbene pentafluorophenyl species [Ru(IEt2Me2)2(PPh3)(C6F5)H] (3). The formation of 3 resulted from C–H activation of C6F5H (formed from C6F6via stoichiometric hydrodefluorination), a process which could be reversed by working under 4 atm H2. Upon heating 1 with C6F5H, the bis-phosphine derivative [Ru(IEt2Me2)(PPh3)2(C6F5)H] (4) was isolated. A more efficient route to 2 involved treatment of 1 with 0.33 eq. of TREAT-HF (Et3N·3HF); excess reagent gave instead the [H2F3]− salt (5) of the known cation [Ru(IEt2Me2)2(PPh3)2H]+. Under catalytic conditions, 1 proved to be an active precursor for hydrodefluorination, converting C6F6 to a mixture of tri, di and monofluorobenzenes (TON = 37) at 363 K with 10 mol% 1 and Et3SiH as the reductant

Mono- and dinuclear Ni(I) products formed upon bromide abstraction from the Ni(I) ring-expanded NHC complex [Ni(6-Mes)(PPh₃)Br]

Bromide abstraction from the three-coordinate Ni(I) ring-expanded N-heterocyclic carbene complex [Ni(6-Mes)(PPh3)Br] (1; 6-Mes = 1,3-bis(2,4,6-trimethylphenyl) 3,4,5,6-tetrahydropyrimidin-2-ylidene) with TlPF6 in THF yields the T-shaped cationic solvent complex, [Ni(6-Mes)(PPh3)(THF)][PF6] (2), whereas treatment with NaBArF4 in Et2O affords the dimeric Ni(I) product, [{Ni(6-Mes)(PPh3)}2(µ-Br)][BArF4] (3). Both 2 and 3 act as latent sources of the cation [Ni(6-Mes)(PPh3)]+, which can be trapped by CO to give [Ni(6-Mes)(PPh3)(CO)]+ (5). Addition of [(Et3Si)2(µ-H)][B(C6F5)4] to 1 followed by work up in toluene results in the elimination of phosphine as well as halide to afford a co-crystallised mixture of [Ni(6-Mes)(η2-C6H5Me)][B(C6F5)4] (4), and [6MesH⋅ C6H5Me][B(C6F5)4]. Treatment of 1 with sodium salts of more strongly coordinating anions leads to substitution products. Thus, NaBH4 yields the neutral, diamagnetic dimer [{Ni(6-Mes)}2(BH4)2] (6), whereas NaBH3(CN) gives the paramagnetic monomeric cyanotrihydroborate complex [Ni(6-Mes)(PPh3)(NCBH3)] (7). Treatment of 1 with NaOtBu/NHPh2 affords the three-coordinate Ni(I) amido species, [Ni(6-Mes)(PPh3)NPh2] (8). The electronic structures of 2, 5, 7 and 8 have been analysed in comparison to that of previously reported 1 using a combination of EPR spectroscopy and density functional theory. <br/

Solar Energetic Particles Produced by a Slow Coronal Mass Ejection at ∼0.25 au

We present an analysis of Parker Solar Probe (PSP) IS⊙IS observations of ~30–300 keV n⁻¹ ions on 2018 November 11 when PSP was about 0.25 au from the Sun. Five hours before the onset of a solar energetic particle (SEP) event, a coronal mass ejection (CME) was observed by STEREO-A/COR2, which crossed PSP about a day later. No shock was observed locally at PSP, but the CME may have driven a weak shock earlier. The SEP event was dispersive, with higher energy ions arriving before the lower energy ones. Timing suggests the particles originated at the CME when it was at ~7.4R_⊙. SEP intensities increased gradually from their onset over a few hours, reaching a peak, and then decreased gradually before the CME arrived at PSP. The event was weak, having a very soft energy spectrum (−4 to −5 spectral index). The earliest arriving particles were anisotropic, moving outward from the Sun, but later, the distribution was observed to be more isotropic. We present numerical solutions of the Parker transport equation for the transport of 30–300 keV n⁻¹ ions assuming a source comoving with the CME. Our model agrees well with the observations. The SEP event is consistent with ion acceleration at a weak shock driven briefly by the CME close to the Sun, which later dissipated before arriving at PSP, followed by the transport of ions in the interplanetary magnetic field